Removal of vanadium and sodium from petroleum hydrocarbons



W- B. PORTER ETAL REMOVAL OF VANADIUM AND SODIUM FROM PETROLEUM HYDROCARBONS Filed Jan. 22, 1953 OF HYDROFNING TO CATALYST REACTOR PLANT 2 uojAUXlTE ZONE FOR VANADIUM REMOVAL .RECYCLE GAS mm HYDROFlNlNG PLANT HEATER Rsc'vcn: GAS

IsT. sAuxn': 26M: FOR somum REMOVAL a INVENT OBS FREDERICK WILLIAM BERTRAM PORTER ROY PURDY NORTHCOTT 7M vylmA-h ATTORNEYS Patented Aug. 31, 1954 REMOVAL OF VANADIUM AND SODIUM FROM PETROLEUM HYDROCARBONS Frederick William Bertram Porter and Roy Purdy Northcott, Sunbury-onThames, England, assignors to Anglo-Iranian Oil Company Limited, London, England, a British joint-stockcorporation Application January 22, 1953, Serial Not 332,662

Claims priority, application Great Britain January 31, 1952 Claims.

This invention relates to the removal of vanadium and sodium from petroleum hydrocarbons in particular crude petroleum and petroleum residues.

In the specification of the co-pending application of Porter and Hyde No. 263,956, filed December 28, 1951, there is described a process for the removal of vanadium and sodium from petroleum hydrocarbons wherein the hydrocarbons are contacted with bauxite in the presence or absence of hydrogen and under conditions of temperature and pressure such that the sodium and vanadium are deposited on or incorporated with the bauxite. The removal of sodium and vanadium from a petroleum feedstock prior to hydrofining the feedstock is of particular advantage since it avoids contamination of the cobalt molybdate type catalyst commonly used in the hydrofining process, and such a two-stage process forms the subject of co-pending application of Porter and Hyde, No. 276,256 filed December 13, 1952. It has now been discovered that the conditions which are most favourable for the removal of vanadium from petroleum feedstocks are not the most favourable for the removal of sodium and vice versa. For example, on treating a Kuwait residue over bauxite at 780 F., 1000 p. s. i. ga., 1.0 v./v./hr. and 4000 SCF/B recycle rate, the vanadium removal over 100 hours was approximately 5 and the sodium removal 3 On treating the same feedstock over bauxite at 780" E, 1000 p. s. 1. ga. and 1.0 v./v./hr. but without hydrogen recycle, vanadium removal was only approximately whereas sodium removal was over 90%. The feedstock employed con;- tained 35 p. p. m. vanadium and 35 p. p. In. sodium, the bulk of the sodium being of extraneous origin introduced during distillation of the crude.

It is considered that vanadium removal is primarily a hydrogenation process which is dependent, among other things, upon the hydrogen partial pressure, while the removal of extraneous or uncombined sodium is primarily a physical process, the efliciency of which is not improved by the presence of hydrogen which competes with the sodium for the adsorbing surface of the bauxite. Whether this explanation is correct or not, it has been discovered that improved removal of vanadium and sodium may be effected by a twostage treatment over bauxite, only one stage being carried out in the presence of hydrogen.

According to the invention therefore, a petroleum feedstock containing vanadium and uncombined sodium is passed first over bauxite at elevated temperature and pressure and in the absence of hydrogen, whereby substantially all the sodium is removed from the feedstock, and then over bauxite at elevated temperature and pressure and in the presence of hydrogen, whereby a considerable proportion of the vanadium is removed from the feedstock.

Both stages of the process are advantageously operated at a temperature of approximately 780 F. and a pressure of approximately 1000 lb./sq. in.

The invention may advantageously be carried into effect in a tower containing a single bed of bauxite, hydrogen being admitted to the tower at an intermediate point calculated to afford the optimum space Velocities for both sodium and vanadium removal.

The invention also includes a continuous process wherein a petroleum feedstock containing vanadium and sodium is passed first to a twostage bauxite treating process as above described and is then passed to a hydrofining zone wherein it is treated for the removal of organically combined sulphur.

One embodiment of the process according to the invention is diagrammatically illustrated in the accompanying drawing.

A petroleum feedstock containing sodium and vanadium, such as crude oil or crude oil residue, is passed via line It and heater H into a tower l2. The treated feedstock leaving the tower I2 is passed via line l3 to a hydrofining zone operated in known manner. The tower I2 is divided into a lower part In and an upper part lZb, both parts being filled with bauxite, and recycle gas from the hydrofining zone is introduced into the tower between the two parts thereof via line 14 and heater l5.

We claim:

l. A process for the removal of vanadium and sodium from petroleum hydrocarbons, which comprises passing the hydrocarbons over bauxite at elevated temperature and pressure and in the absence of hydrogen, whereby substantially all the sodium is removed from the hydrocarbons, and then passing the hydrocarbons over bauxite at elevated temperature and pressure and in the presence of hydrogen, whereby a considerable proportion of the vanadium is removed from the hydrocarbons.

2. A process according to claim 1, wherein both stages of the process are operated at a temperature of approximately 780 F. and a pressure of approximately 1000 1b./sq. in.

3. A process for the removal of vanadium and sodium from petroleum hydrocarbons, which comprises passing the hydrocarbons through a bed of bauxite at elevated temperature and pressure, and admitting hydrogen to said bed at an intermediate point calculated to afiord optimum space velocities for both sodium and vanadium removal.

4. A process according to claim 3, wherein the bed of bauxite is maintained at a temperature of approximately 780 F. and a pressure of approximately 1000 1b./sq. in.

5. A process for the treatment of petroleum 0 hydrocarbons containing vanadium, sodium and organically combined sulphur, which comprises passing the hydrocarbons over bauxite at elevated temperature and pressure and in the absence of 5 combined sulphur.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,753,859 Gray Apr. 8, 1930 2,340,939 Davis et al Feb. 8, 1942 2,41 ,029 Oberfell Apr, 15, 1947 2,614,068 Healy et al Oct. 14, 1952 

1. A PROCESS FOR THE REMOVAL OF VANADIUM AND SODIUM FROM PETROLEUM HYDROCARBONS, WHICH COMPRISES PASSING THE HYDROCARBONS OVER BAUXITE AT ELEVATED TEMPERATURE AND PRESSURE AND IN THE ABSENCE OF HYDROCARBON, WHEREBY SUBSTANTIALLY ALL THE SODIUM IS REMOVED FROM THE HYDROCARBONS AND THEN PASSING THE HYDROCARBONS OVER BAUXITE AT ELEVATED TEMPERATURE AND PRESSURE AND IN THE PRESENCE OF HYDROGEN, WHEREBY A CONSIDERABLE PROPORTION OF THE VANDIUM IS REMOVED FROM THE HYDROCABRONS. 